CN102000516B - Method for preparing polydimethylsiloxane (PDMS)/polyvinylidene fluoride (PVDF) composite hollow fiber film - Google Patents
Method for preparing polydimethylsiloxane (PDMS)/polyvinylidene fluoride (PVDF) composite hollow fiber film Download PDFInfo
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- CN102000516B CN102000516B CN2010102986642A CN201010298664A CN102000516B CN 102000516 B CN102000516 B CN 102000516B CN 2010102986642 A CN2010102986642 A CN 2010102986642A CN 201010298664 A CN201010298664 A CN 201010298664A CN 102000516 B CN102000516 B CN 102000516B
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Abstract
The invention discloses a method for preparing a polydimethylsiloxane (PDMS)/polyvinylidene fluoride (PVDF) composite hollow fiber film, which comprises the following steps: (1) dissolving polydimethylsiloxane in normal hexane, adding a crosslinking agent, mixing, stirring for 0.5 to 2 hours, adding a catalyst, supplementing normal hexane till the polydimethylsiloxane mass percentage concentration of the mixed solution is 5 to 30 percent, stirring at room temperature for 8 to 16 hours, centrifuging, defoaming and preparing film solution, wherein the crosslinking agent is tetraethoxysilane, the mass ratio of the crosslinking and the polydimethylsiloxane is 0.06-0.1:1, the catalyst is dibutyltin dilaurate, and the mass ratio of the catalyst to the polydimethylsiloxane is 0.01-0.05:1; and (2) immersing a dried neutral polyvinylidene fluoride hollow fiber base film in the film-making solution for 2 to 3 seconds, taking the base film out, drying the base film at room temperature, repeating the film immersing and drying operation for 2 to 3 times, and drying under vacuum at 30 to 110 DEG C till complete crosslinking. In the invention, the process is simple; and the obtained hollow fiber film has an excellent separation effect on low-concentration ketone/butanol/ethanol solution.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the organic PDMS/PVDF of infiltration evaporation penetrated preferably (dimethyl silicone polymer/Kynoar) composite hollow fiber membrane, belong to the infiltrating and vaporizing membrane separation field.
Background technology
As far back as 1861, Pasteur just found that bacterium can produce butanols.By 1945, the U.S. had 2/3 butanols to produce through biological fermentation process.But to the sixties in 20th century, because the fermentation raw material price is high, production concentration is low, the product recovery cost is high, and under the impact of petroleum chemical industry, the biological butanol industry is made slow progress.Oil crisis appearred up to 1973, oil shortage, and ballooning oil prices makes biological butanol receive people's attention again.
Utilize clostridium acetobutylicum to produce in the zymotic fluid of butanols except containing butanols, also contain acetone and a spot of ethanol (being commonly called as the ABE fermentation).Because butanols and acetone is to the toxic effect of microorganism, when product reached certain concentration, microorganism stopped growing, and tangible product inhibition phenomenon occurs, and this is the immediate cause that causes tunning concentration low.Therefore, must adopt effective method that product A BE is separated from zymotic fluid, ABE in the zymotic fluid is controlled at very low concentration, reduce product and suppress, improve productive rate and yield, and reduce the later separation cost.(Maddox such as the technology that being applied to of having studied separated ABE comprises that absorption, gas are carried, liquid-liquid extraction, infiltration extraction, counter-infiltration and infiltration evaporation; I.S.The acetone-butanol-ethanol fermentation:Recent progress in technology [J] .Biotechnol.Genet.Eng.Rev.1989; 7; 189-220); Wherein infiltration evaporation since advantages such as its high selectivity, economy, simplicity obtain extensive studies (Tong Cancan, Yang Lirong, Wu Jian equality. the progress of acetone separation coupling technology [J]. the chemical industry progress.2008，27(11)：1783-1789)。
Infiltration evaporation (pervaporation PV) is up-and-coming youngster in the membrane separation technique, to azeotropic and difficulty such as closely boil divide system to have superior stalling characteristic, be considered to be hopeful most to replace a kind of separation method of rectifying.Infiltration evaporation have in separation is big, centrifugation does not receive the component vapour-liquid equilibrium restriction, the process do not introduce other reagent, process is simple and operate advantages such as more convenient.
The infiltrating and vaporizing membrane that is applied to acetone/ethanol separation at present mainly contains the high molecular polymerization film, inoranic membrane and liquid film.Polyethers copolyamide (PEBA) is a kind of important macromolecular material, and the polymeric membrane that makes thickness 100 μ m with it to the separating effect of binary system (acetone-water, butanols-water, alcohol-water) is: separation factor alpha
Acetone=4.2, α
Butanols=8.2 and α
Ethanol=2.4, corresponding total permeation flux is respectively 27.4gm
-2h
-1, 65.3gm
-2h
-1And 37.2gm
-2h
-1(Liu, FF; Liu, L; Feng, XS.Separation of acetone-butanol-ethanol (ABE) from dilute aqueous solution by pervaporation [J] .Sep.Purif.Technol.2005,42 (3): 273-282); Inoranic membrane is because material price is expensive, liquid film has been because inferior positions such as poor stability have limited their application in industry.
Above-mentioned film is flat sheet membrane basically, and its mechanical strength is not high, and the membrane area of unit volume is less, and the membrane module floor space is big, is not easy to industrial applications.Hollow-fibre membrane is compact conformation then, and the membrane area of unit volume is big, and self-cradling type has remarkable advantages on commercial Application.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of PDMS/PVDF composite hollow fiber membrane.
For realizing above-mentioned purpose, the technical scheme that the present invention taked is: the preparation method of this PDMS/PVDF composite hollow fiber membrane may further comprise the steps:
(1) dimethyl silicone polymer is dissolved in the n-hexane; The back adds crosslinking agent and mixes stirring 0.5～2 hour; Add catalyst again; It is 5～30% that the back replenishes the mass percent concentration that adds dimethyl silicone polymer in n-hexane to the mixed liquor, stirring at room 8～16 hours, and preparation liquid is processed in centrifugal, deaeration; Said crosslinking agent is an ethyl orthosilicate, and the mass ratio of said crosslinking agent and dimethyl silicone polymer is 0.06～0.1: 1; Said catalyst is a dibutyl tin laurate, and the mass ratio of said catalyst and dimethyl silicone polymer is 0.01～0.05: 1;
The neutral Kynoar doughnut basement membrane that (2) will dry immersed in the said preparation liquid 2～3 seconds; The back is taken out and is at room temperature dried; Repeat above-mentionedly to soak film, dry operation 2～3 times; It is extremely crosslinked fully 30～110 ℃ of following vacuum drying to put into vacuum drying oven then, makes the PDMS/PVDF composite hollow fiber membrane.
Compared with prior art, the present invention prepares that the technology of PDMS/PVDF composite hollow fiber membrane is simple, easy to operate, production cost is lower.The PDMS separating layer of prepared PDMS/PVDF composite hollow fiber membrane outer surface densification is good to acetone/ethanol selectivity; Separation factor is high; The effect of the crosslinking agent ethyl orthosilicate that hydrophobicity is moderate has guaranteed considerable flux, can be used for the separation of acetone/alcohol fermentation liquid; The hydrophobic PVDF supporting layer of this film inner surface has excellent mechanical intensity, can play the self-supporting effect.And the injury of PDMS, PVDF material pair cell avirulence is difficult for contaminatedly, so this film can be processed into hollow fiber film assembly, directly with the fermentation system coupling, realizes that acetone butanol fermentation separates the industrialization that is coupled.
The specific embodiment
Below in conjunction with instantiation technical scheme of the present invention is done further explanation.
Embodiment 1:
Claim that 10g dimethyl silicone polymer (PDMS) is dissolved in the 100g n-hexane; Add 0.6g crosslinking agent ethyl orthosilicate; Mix under the room temperature to stir and add 0.1g catalyst dibutyl tin laurate after 0.5 hour; The concentration that adds dimethyl silicone polymer in n-hexane to the mixed liquor is 5wt%, sealing back stirring at room 8 hours, and gained solution is processed preparation liquid through centrifugal, deaeration.Kynoar (PVDF) hollow-fibre membrane is extremely neutral with distilled water flushing, and room temperature is dried, and is for use as basement membrane.This basement membrane of handling was immersed in preparation liquid 2～3 seconds, take out the back room temperature and dry.Repeat to film 3 times, put into then vacuum drying oven 110 ℃ of following vacuum drying 10 hours to crosslinked fully, make the PDMS/PVDF composite hollow fiber membrane.The skin of gained composite hollow fiber membrane is fine and close PDMS separating layer, and internal layer is hydrophobic PVDF supporting layer.The PDMS/PVDF composite hollow fiber membrane of present embodiment gained is carried out organic solvent infiltration evaporation separating experiment, and performance is as shown in table 1:
Table 1
Annotate: test condition: 40 ℃ of temperature, downstream vacuum 0.3KPa.
Embodiment 2:
Claim that the 10g dimethyl silicone polymer is dissolved in the 50g n-hexane; Add 1.0g crosslinking agent ethyl orthosilicate; Mix under the room temperature to stir and add 0.5g catalyst dibutyl tin laurate after 1 hour; The concentration that adds dimethyl silicone polymer in n-hexane to the mixed liquor is 15wt%, sealing back stirring at room 12 hours, and gained solution is processed preparation liquid through centrifugal, deaeration.The PVDF hollow-fibre membrane is extremely neutral with distilled water flushing, and room temperature is dried, and is for use as basement membrane.This basement membrane of handling was immersed in preparation liquid 2～3 seconds, take out the back room temperature and dry.Repeat to film 3 times, put into then vacuum drying oven 30 ℃ of following vacuum drying 10 hours to crosslinked fully, make the PDMS/PVDF composite hollow fiber membrane.The skin of gained composite hollow fiber membrane is fine and close PDMS separating layer, and internal layer is hydrophobic PVDF supporting layer.The PDMS/PVDF composite hollow fiber membrane of present embodiment gained is carried out organic solvent infiltration evaporation separating experiment, and performance is as shown in table 2:
Table 2
Annotate: test condition: 40 ℃ of temperature, downstream vacuum 0.3KPa.
Embodiment 3:
Claim that the 20g dimethyl silicone polymer is dissolved in the 50g n-hexane; Add 1.6g crosslinking agent ethyl orthosilicate; Mix under the room temperature to stir and add 0.6g catalyst dibutyl tin laurate after 2 hours; The concentration that adds dimethyl silicone polymer in n-hexane to the mixed liquor is 30wt%, sealing back stirring at room 16 hours, and gained solution is processed preparation liquid through centrifugal, deaeration.The PVDF hollow-fibre membrane is extremely neutral with distilled water flushing, and room temperature is dried, and is for use as basement membrane.This basement membrane of handling was immersed in preparation liquid 2～3 seconds, take out the back room temperature and dry.Repeat to film 2 times, put into then vacuum drying oven 80 ℃ of following vacuum drying 10 hours to crosslinked fully, make the PDMS/PVDF composite hollow fiber membrane.The skin of gained composite hollow fiber membrane is fine and close PDMS separating layer, and internal layer is hydrophobic PVDF supporting layer.The PDMS/PVDF composite hollow fiber membrane of present embodiment gained is carried out organic solvent infiltration evaporation separating experiment, and performance is as shown in table 3:
Table 3
Annotate: test condition: 40 ℃ of temperature, downstream vacuum 0.3KPa.
Can know by table 1 to table 3; In low solvent strength scope (ABE concentration range in the ABE zymotic fluid); The separation factor of butanols and acetone has reached 10～30; The separation factor of ethanol is about 4, and corresponding total permeation flux is also higher, and visible PDMS/PVDF composite hollow fiber membrane of the present invention has separating effect preferably to the acetone/ethanolic solution of low concentration.
Claims (1)
1. the preparation method of dimethyl silicone polymer/Kynoar composite hollow fiber membrane is characterized in that this method may further comprise the steps:
(1) dimethyl silicone polymer is dissolved in the n-hexane; The back adds crosslinking agent and mixes stirring 0.5～2 hour; Add catalyst again; It is 5～30% that the back replenishes the mass percent concentration that adds dimethyl silicone polymer in n-hexane to the mixed liquor, stirring at room 8～16 hours, and preparation liquid is processed in centrifugal, deaeration; Said crosslinking agent is an ethyl orthosilicate, and the mass ratio of said crosslinking agent and dimethyl silicone polymer is 0.06～0.1 ︰ 1; Said catalyst is a dibutyl tin laurate, and the mass ratio of said catalyst and dimethyl silicone polymer is 0.01～0.05 ︰ 1;
The neutral Kynoar doughnut basement membrane that (2) will dry immersed in the said preparation liquid 2～3 seconds; The back is taken out and is at room temperature dried; Repeat above-mentionedly to soak film, dry operation 2～3 times; It is extremely crosslinked fully 30～110 ℃ of following vacuum drying to put into vacuum drying oven then, makes dimethyl silicone polymer/Kynoar composite hollow fiber membrane.
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| CN102728248A (en) * | 2012-07-12 | 2012-10-17 | 广州同胜环保科技有限公司 | Preparation method of organic composite membrane and application of organic composite membrane |
| CN104069751A (en) * | 2014-07-19 | 2014-10-01 | 陈雄 | Preparation method for PDMS (polydimethylsiloxane)/PTFE polytetrafluoroethylene pervaporation hollow-fiber membrane |
| CN104084052B (en) * | 2014-07-28 | 2016-08-24 | 陈雄 | A kind of preparation method of silicone rubber composite hollow fiber membrane |
| CN104138717B (en) * | 2014-08-14 | 2016-08-17 | 娄尤来 | A kind of preparation method of PDMS/PAN infiltration evaporation hollow-fibre membrane |
| CN104147947B (en) * | 2014-08-14 | 2016-08-24 | 娄尤来 | A kind of preparation method of PDMS/PAN composite hollow fiber membrane |
| CN105126631B (en) * | 2015-08-30 | 2017-04-12 | 广州益昌塑料有限公司 | Preparation method for PDMS/BC/PVDF hollow fibrous membranes |
| CN104998561B (en) * | 2015-08-30 | 2017-05-03 | 广州加泰医药科技有限公司 | Preparation method of silicone rubber membrane |
| KR102115434B1 (en) * | 2019-12-24 | 2020-05-28 | 주식회사 퓨어엔비텍 | Ultrahydrophobic composite membrane for a membrane aerated biofilm reactor process and preparation method thereof |
| CN111675907A (en) * | 2020-05-06 | 2020-09-18 | 云南电网有限责任公司 | Method for preparing high-temperature-resistant heat-insulating silicone rubber by using waste hollow fiber membranes |
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